WO2005116094A1 - Polymerisation d'isobutene en presence de complexes d'un donneur avec des acides fluores - Google Patents

Polymerisation d'isobutene en presence de complexes d'un donneur avec des acides fluores Download PDF

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Publication number
WO2005116094A1
WO2005116094A1 PCT/EP2005/005093 EP2005005093W WO2005116094A1 WO 2005116094 A1 WO2005116094 A1 WO 2005116094A1 EP 2005005093 W EP2005005093 W EP 2005005093W WO 2005116094 A1 WO2005116094 A1 WO 2005116094A1
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Prior art keywords
isobutene
donor
stands
polymerization
electron donor
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PCT/EP2005/005093
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German (de)
English (en)
Inventor
Mirjam Herrlich-Loos
Christian Drohmann
Darijo Mijolovic
Thomas Wettling
Helmut Mach
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Basf Aktiengesellschaft
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Priority to US11/597,274 priority Critical patent/US7932332B2/en
Priority to DE502005010046T priority patent/DE502005010046D1/de
Priority to EP05743534A priority patent/EP1753793B1/fr
Priority to AT05743534T priority patent/ATE476453T1/de
Publication of WO2005116094A1 publication Critical patent/WO2005116094A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/08—Butenes
    • C08F10/10—Isobutene

Definitions

  • the invention relates to a process for the polymerization of isobutene in the liquid phase.
  • the polymerization of isobutene to give essentially mono-ethylenically unsaturated polyisobutenes is known.
  • the double bond can occupy different positions in the macromolecule, which differ in their reactivity.
  • Highly reactive polyisobutenes can e.g. B. by boron trifluoride-catalyzed polymerization of isobutene or isobutene-containing hydrocarbon streams.
  • boron trifluoride there is a side reaction to the addition of fluorine to the polyisobutene or to the formation of low- and medium-molecular fluorine-containing by-products, such as tert-butyl fluoride, diisobutyl fluoride or triisobutyl fluoride, which contaminate the polyisobutene.
  • EP 322 241 describes a process for the preparation of highly reactive polyisobutenes, in which isobutene is polymerized in the presence of boron trifluoride and a cocatalyst and the polymerization product is immediately quenched.
  • boron trifluoride As a cocatalyst, 35 z. B. hydrogen fluoride.
  • EP 337 737 discloses a process for the preparation of poly-n-butenes, in which 1-butene, ice and / or trans-2-butene are polymerized in the presence of boron trifluoride and hydrogen fluoride.
  • WO 89/01001 discloses a process for oligomerizing lower alkenes in the presence of a catalyst system which contains boron trifluoride and an acid, e.g. B. phosphoric acid.
  • WO 95/26814 describes supported Lewis acid catalysts which are said to be suitable for the catalysis of hydrocarbon conversions such as olefin polymerizations and which contain certain salts of superacids.
  • the complex catalyst preparation is disadvantageous; precautions must also be taken to keep the catalyst suspended uniformly in the reaction mixture.
  • the invention is based on the object of specifying a process which allows the production of highly reactive isobutene polymers with a low fluorine content.
  • This object is achieved by a process for the preparation of essentially mono-ethylenically unsaturated isobutene polymers, in which the sum of the proportions of the molecules with a and the molecules with a double bond is at least 75 mol%, by polymerization of isobutene in the liquid phase in Presence of a dissolved or dispersed catalyst complex which comprises (i) an electron donor and (ii) a compound of the general formula I.
  • Me stands for a metal of the oxidation state m
  • M stands for an element of the oxidation number n selected from among the elements of group 2, 3, 4, 5, 10, 11, 13, 14 or 15 of the periodic table of the elements according to IUPAC notation
  • a stands for an integer> 1
  • b stands for an integer> 1
  • x stands for an integer> 2
  • c stands for [(a + mb) / (xn)].
  • Isobutene polymer is understood to mean polymers which are composed of at least 50% by weight of monomer units which are derived from isobutene.
  • Preferred isobutene polymers comprise at least 80% by weight, preferably at least 90% by weight and in particular at least 95% by weight, of monomer units derived from isobutene. If available, the monomer units other than isobutene are derived from ethylenically unsaturated monomers which are copolymerizable with isobutene under conditions of cationic polymerization.
  • vinyl aromatics such as styrene, CC 4 -alkylstyrenes such as 2-, 3- and 4-methylstyrene, and also 4-tert-butylstyrene, isoolefins with 5 to 10 carbon atoms such as 2-methylbutene-1, 2-methylpentene-1, 2-methylhexene-1, 2-ethylpentene-1, 2-ethylhexene-1 and 2-propylheptene-1, and dienes such as 1, 3-butadiene and isoprene.
  • vinyl aromatics such as styrene, CC 4 -alkylstyrenes such as 2-, 3- and 4-methylstyrene, and also 4-tert-butylstyrene, isoolefins with 5 to 10 carbon atoms such as 2-methylbutene-1, 2-methylpentene-1, 2-methylhexene-1, 2-ethylpentene-1, 2-ethylhex
  • olefins which have a silyl group such as 1-trimethoxysilylethene, 1- (trimethoxysilyl) propene, 1- (trimethoxysilyl) -2-methylpropene-2, 1- [tri (methoxyethoxy) silyl] ethene, are also suitable, 1- [tri (methoxyethoxy) silyl] propene and 1- [tri (methoxyethoxy) silyl] -2-methylpropene-2.
  • Suitable isobutene sources for the process according to the invention are both isobutene itself and isobutene-containing C 4 hydrocarbon streams, for example C 4 raffinates, C cuts from isobutane dehydrogenation, C 4 cuts from steam crackers, FCC crackers (Fluid Catalysed Cracking ), which are preferably largely freed from the 1,3-butadiene contained therein.
  • Suitable C 4 hydrocarbon streams generally contain less than 1000 ppm, preferably less than 200 ppm, of butadiene.
  • the sum of the proportions of isobutane, butane, 1-butene, ice and trans-2-butene in the C 4 hydrocarbon streams is in the range from 20 to 90% by weight, mostly 40 to 70% by weight, where 10 to 70% by weight (based on the total weight of the stream) can be accounted for by the butenes other than isobutene.
  • Such C 4 hydrocarbon streams are preferred feedstocks for the process according to the invention.
  • a mixture of pure isobutene with a non-olefinic diluent is also suitable as the isobutene source.
  • the polymerization takes place in the liquid phase, ie under pressure and temperature conditions at which the reaction mixture is at least partially in condensed liquid form.
  • the reaction mixture usually comprises a diluent or diluent mixture which is essentially inert to the reagents used.
  • Suitable diluents are saturated aliphatic or cycloaliphatic hydrocarbons, such as butane, pentane, hexane, heptane, octane, cyclopentane, cyclohexane, methylcyclohexane; aromatic hydrocarbons such as toluene or ethylbenzene; unsaturated hydrocarbons such as ethylene, 1-butene, 2-butene, halogenated hydrocarbons such as methyl chloride, dichloromethane or trichloromethane, and mixtures of the aforementioned compounds.
  • the solvents are preferably freed from oxygen-containing impurities such as carbon monoxide, water, acetone, carboxylic acids or acidic impurities such as mineral acids, for example by adsorption on solid adsorbents such as activated carbon, molecular sieves or ion exchangers.
  • oxygen-containing impurities such as carbon monoxide, water, acetone, carboxylic acids or acidic impurities such as mineral acids
  • solid adsorbents such as activated carbon, molecular sieves or ion exchangers.
  • the hydrocarbons other than isobutene assume the role of an essentially inert diluent.
  • an unsupported catalyst is used which is dissolved or dispersed or emulsified in the liquid reaction mixture.
  • the catalyst comprises a compound of formula (I) above.
  • Me is optional;
  • Preferred compounds of the formula (I) correspond to the formula H a [MF x ], where M, a and x have the
  • the catalyst is essentially free of compounds of the formula MF X .-
  • Compounds of the formula MF x _ ⁇ (such as in particular BF 3 ) are known to be catalysts for the polymerization of isobutene; their presence means that the advantages of the present invention are not fully realized.
  • the central atom M of the fluorine acid stands for an element selected from among the elements of group 2, 3, 4, 5, 10, 11, 13, 14 or 15 of the periodic table of the elements according to IUPAC notation, preferably for Be, B, AI, Si , P, Ti, V, Ga, Ge, As, Y, Zr, Nb, In, Sn or Sb, in particular for Be, B, AI, Si or P and particularly preferably for B.
  • Me is not critical.
  • Me is preferably an alkali metal, such as Li, Na, K, an alkaline earth metal, such as Ca, or Ag or Au.
  • H a Meb [MF x ] c is selected from H 2 BeF4, HBF 4 , HPF 6 , H 2 SiF 6 , HMeSiF 6 , HAIF 4 , HsAIFe, where Me stands for Li, Na or K.
  • the electron donor (hereinafter also referred to as "donor") contains at least one hetero atom with a free electron pair, for example an oxygen, nitrogen, sulfur and / or phosphorus atom, preferably an oxygen, nitrogen and / or sulfur atom, in particular an oxygen - and / or nitrogen atom
  • the donor has no active hydrogen atoms, i. H. especially no hydrogen atoms bound to an oxygen or nitrogen atom.
  • Suitable oxygen-containing donors are alcohols, ketones, ethers, carboxylic acids and / or carboxylic acid esters.
  • Suitable alcohols include, for example, CrC 13 alkanols and C 5 -C 6 cycloalkanols or C 2 -C 10 alkanediols, such as methanol, ethanol, n-propanol, isopropanol, 2-butanol, t-butanol, 2-ethylhexanol; cyclohexyl alcohol; Ethylene glycol or propylene glycol.
  • Suitable ketones include acetone, ethyl methyl ketone, acetoacetone or acetophenone.
  • C 2 -C 20 dialkyl ethers come as ethers; Cyclic ethers, in particular 5- or 6-membered cyclic ethers with one or two oxygen atoms in the ring, such as tetrahydrofuran or dioxane, into consideration.
  • Suitable carboxylic acids or esters are acetic acid, propionic acid, butyric acid, caproic acid, benzoic acid or esters thereof, e.g. B. the methyl or ethyl ester.
  • Nitrogen-containing donors such as ammonia, organic amines or polyamines or hydroxylamine are also suitable. Nitrile compounds or amides.
  • Exemplary organic amines are methylamine, dimethylamine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, diisopropylamine, 2-ethylhexylamine, diisobutylamine, sec-butylamine, tert-butylamine, tri-n-octylamine, di-2-ethylhexylamine, allylamine, Diallylamine, triallylamine, aniline, benzylamine, ethylenediamine, hexamethylenediamine, tretramethylethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylpentamine, 3- (methylamino) propylamine, 3- (dimethylamino) propylamine and 3- (dibutylamino) propylamine; Oxyamines such as 3-methoxypropylamine, 3-ethoxypropylamine, and 3- (2
  • Exemplary nitrile compounds are acetonitrile, propionitrile and benzonitrile.
  • Exemplary amides are formamide, dimethylformamide, acetamide, dimethylacetamide, propionamide, benzamide, N, N-dimethylbenzamide.
  • sulfur-containing donors are thiols, such as dodecyl mercaptan, thioethers, dialkyl disulfides, or sulfoxides, such as dimethyl sulfoxide, sulfones, sulfonic acid esters, such as methylsulfonic acid methyl ester, dialkyl sulfates, such as dimethyl sulfate.
  • Suitable phosphorus-containing donors are phosphines, such as triphenylphosphine,
  • Suitable ligands are polymeric ligands, such as polyvinyl alcohol, polyvinylamine, polyethers, such as polyalkylene glycols, for. B. polyethylene glycols, polyalkylene glycol mono- or dialkyl ethers, polyalkylene amines such as polyethylene amines, polyalkyleneimines, for. B. polyethyleneimines with molecular weights of preferably 300 to 20,000, in particular from 300 to 5,000, polyamides, such as nylon 6 or nylon 6,6, and aliphatic or aromatic polyketones.
  • polymeric ligands such as polyvinyl alcohol, polyvinylamine, polyethers, such as polyalkylene glycols, for.
  • the ligand is generally selected from alcohols, ketones, ethers, amines, nitriles, amides and sulfoxides.
  • the donor comprises a first donor L 1 and a second donor L 2 , where L is an ether and L 2 is selected from alcohols, carboxylic acids, carboxylic acid esters, amines, nitriles, amides and sulfoxides.
  • Preferred donors L 1 are selected from ethers of the formula ROR ', where R and R' independently of one another are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl or tert-butyl. At least one of the radicals R and R 'is preferably methyl.
  • the donor comprises a first donor L 1 and a second donor L 2 , L 1 being an ether different from a tertiary alkyl ether and L 2 among alcohols, tertiary alkyl ethers, carboxylic acids, carboxylic esters, amines, nitriles, amides and sulfoxides is selected.
  • Preferred donors L 1 are selected from ethers of the formula ROR ', where R and R' independently of one another are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or s-butyl.
  • R and R ' is methyl; Dimethyl ether is particularly preferred.
  • Preferred donors L 2 are methyl tert-butyl ether, diisopropyl ether, methanol, dimethylformamide, dimethyl sulfoxide.
  • the donor L 1 is present in at least a stoichiometric amount, e.g. B. in an amount of 0.8 to 1, 2 molar equivalents, based on the element M before.
  • the donor L 2 is preferably present in an amount of up to 0.4, preferably 0.001 to 0.15 molar equivalents, based on the element M.
  • a particularly preferred catalyst comprises HBF 4 • O (CH 3 ) 2 , optionally in combination with a further electron donor, in particular those described above as L 2 .
  • the concentration of the catalyst in the reactor in the production of isobutene polymers having number average molecular weights in the range from 200 to 5000 is, for example, 0.01 to 3% by weight, based on the liquid reaction phase; in the production of isobutene polymers with number average molecular weights in the range from 5000 to 50,000, for example 0.001 to 0.01% by weight.
  • the catalysts used according to the invention can be produced in any expedient manner. They can be prefabricated or generated in situ in the polymerization mixture.
  • the catalyst complexes can be pre-formed in separate reactors before being used in the process according to the invention, stored temporarily after their formation and metered into the polymerization apparatus as required. This variant is preferred.
  • a fluorine acid is complexed with the selected donor or the fluorine acid is dissolved therein.
  • tetrafluoroboric acid can be reacted with dimethyl ether.
  • the fluorine acid can in turn be obtained by reacting a fluorine compound of the formula MF x _ ⁇ with hydrogen fluoride HF, for. B. by implementing
  • a complex consisting of the fluorine compound and a donor is reacted with hydrogen fluoride.
  • a boron trifluoride etherate e.g. B. boron trifluoride dimethyl etherate or boron fluoride diethyl etherate, react with hydrogen fluoride, the catalyst being obtained.
  • the reactions are preferably carried out in bulk or alternatively in an inert solvent such as the diluent mentioned above.
  • the hydrogen fluoride can be used in gaseous form or in the form of a solution in an inert solvent.
  • Another variant is to generate the catalyst complexes in situ in the polymerization apparatus. In this procedure, either (i) the donor and, separately, the acid H a MF x , or
  • the donor and hydrogen fluoride are fed into the polymerization apparatus in separate streams and dissolved or dispersed in the reaction mixture.
  • the components are converted into a catalytically active complex.
  • the components are expediently dissolved in a suitable solvent and fed into the reaction mixture in the form of a solution.
  • isobutene or the reaction mixture of unreacted isobutene and polyisobutene can act as a solvent in the in situ generation of the catalyst complex.
  • the donors can be premixed or separated from one another at different stages of the catalyst. gate formation can be added. It is sometimes expedient to meter a pre-formed complex comprising a fluorine acid and a first donor and a second donor into the polymerization mixture in separate streams.
  • the catalytically active complex is finely dispersed in the reaction mixture.
  • the fine dispersion is carried out using suitable devices, such as stirrers, preferably high-speed stirrers, static mixers, orifices for reducing the cross section, mixing pumps and the like.
  • the polymerization according to the invention can also be carried out in the presence of a fluoride scavenger.
  • Suitable fluoride scavengers are organosilicon compounds which have at least one Si-O, Si-C, Si-H bond or a bond from a silicon atom to a halogen atom other than fluorine.
  • Suitable organosilicon compounds are e.g. B. phenyltrimethylsilane, phenyltrichlorosilane or trimethylsilane.
  • organosilicon compounds are those of the general formula II:
  • n 1, 2 or 3
  • R a can be the same or different and, independently of one another, C
  • R b are the same or different and are -CC 2 o-alkyl or for
  • n 1 or 2
  • two radicals R together can represent alkylene.
  • n is preferably 1 or 2.
  • R a preferably denotes a C C ⁇ -alkyl group, and in particular a branched alkyl group or an alkyl group bonded via a secondary C atom, such as isopropyl, isobutyl, 2-butyl, or a 5-, 6- or 7- membered cycloalkyl group, or an aryl group.
  • the variable R b preferably represents a CC 4 alkyl group or a phenyl, tolyl or benzyl radical.
  • Examples of such preferred compounds are dimethoxydiisopropylsilane, dimethoxyisobutylisopropylsilane, dimethoxydiisobutylsilane, dimethoxydicyclopentylsilane, Dimethoxyisobutyl-2-butylsilane, diethoxyisobutylisopropylsilane, triethoxytoluylsilane, triethoxybenzylsilane and triethoxyphenylsilane.
  • the polymerization can be carried out batchwise or preferably continuously.
  • part of the reaction mixture formed in the polymerization reactor is continuously discharged.
  • a quantity of feed materials corresponding to the discharge is fed continuously to the polymerization reactor.
  • the circulation / inflow ratio, i.e. H. the ratio of the amount of substance in the polymerization reactor to the amount that is discharged is generally in the range from 1000: 1 to 1: 1, preferably in the range from 500: 1 to 5: 1 and in particular in the range from 20: 1 to 100: 1 vol./ol.
  • the average residence time of the monomers to be polymerized in the polymerization reactor can be 5 seconds to several hours. Residence times of 1 to 30 minutes, in particular 2 to 20 minutes, are preferred.
  • the polymerization takes place in the reactors customary for continuous polymerization, such as stirred tanks, tube, tube bundle and loop reactors, loop reactors, ie. H. Tube (bundle) reactors with circulation and turbulent flow or installations such as static mixers, d. H. with stirred tank characteristics are preferred. Loop reactors with tube cross sections that lead to turbulent flow are particularly favorable. Reactors connected in series can be used, in particular arrangements of main and post-reactors.
  • the polymerization is generally carried out at a temperature in the range from -60 ° C to +40 ° C, preferably less than 0 ° C, particularly preferably in the range from -5 ° C to -40 ° C and especially in the range from -10 ° C to -30 ° C.
  • the heat of polymerization is removed accordingly with the aid of a cooling device. This can be operated, for example, with liquid ammonia as a coolant.
  • the polymerization process according to the invention is preferably carried out under isothermal conditions, i.e. the temperature of the liquid reaction mixture in the polymerization reactor has a stationary value and does not change or changes only to a small extent during the operation of the reactor.
  • the stationary concentration of the isobutene in the liquid reaction phase is 0.2 to 50% by weight, preferably 0.5 to 20 wt .-% and in particular 1 to 10 wt .-%, based on the liquid reaction phase.
  • the polymerization is carried out in its simplest embodiment in two polymerization stages.
  • the discharge from the first polymerization stage is preferably passed directly into the second polymerization stage.
  • the polymerization is continued without the addition of fresh isobutene.
  • the second polymerization stage is advantageously operated at the same or a lower polymerization temperature than the first polymerization stage, as a rule the temperature difference is 0 to 20 ° C., preferably 0 to 10 ° C.
  • the isobutene conversion in the second polymerization stage is set such that the total conversion of the isobutene in the first and second polymerization stages is generally from 80 to 100%, preferably from 90 to 100%, in particular from 95 to 100%.
  • the unreacted isobutene can alternatively be carried out together with the polymerization output from the second polymerization stage without further working up a third polymerization stage are supplied and further polymerized there up to an isobutene content of less than 2% by weight.
  • the reaction mixture discharged from the polymerization reactor still contains polymerizable monomers and catalyst. As a rule, therefore, the polymerization also proceeds in the discharge. As a result, the polymer formed in the polymerization reactor can be disadvantageous in terms of molecular weight, molecular weight distribution and Change end group content.
  • the polymerization is therefore usually terminated by deactivating the catalyst. Deactivation can be effected, for example, by adding water, alcohols, acetonitrile, ammonia or aqueous solutions of mineral bases or by initiating the discharge into one of the aforementioned media. Deactivation with water is preferred, which is preferably carried out at temperatures in the range from 1 to 80 ° C. (water temperature).
  • the complex catalysts can also be largely separated from the discharge and returned to the polymerization reaction.
  • the reaction mixture e.g. B. in a phase separation vessel flowed through at a slow speed
  • the finely divided droplets of the catalyst coalesce rapidly and pass into a coherent phase.
  • the complex droplets or the coherent phase have a significantly higher density than the polymer solution. They can therefore generally be separated from the polymer-rich, low-catalyst product phase with the aid of separators, separators or other collecting containers.
  • a filtering device which converts small hydrophilic complex droplets into larger drops via suitable pore diameters and / or hydrophilic filter material, can improve the formation of a coherent catalyst phase.
  • Glass fibers, phenolic resins or phenolic resin coatings are often used as the hydrophilic filter material, but acrylonitrile fibers or coatings are also suitable here.
  • This coalescence is often supported by a separator, in this case hydrophobic filtration.
  • a hydrophobic filter material possibly in combination with a narrow pore diameter, prevents the passage of finely dispersed catalyst pots.
  • the polymer-rich product phase separated from the catalyst phase is generally homogeneous and only contains small amounts of soluble catalyst components. These are deactivated in the manner described above, preferably with water.
  • the sum of the proportions of the molecules with - and ⁇ -double bond (based on the number of all olefinically unsaturated macromolecules in a sample) in the polyisobutene obtained by the process according to the invention is at least 75 mol%, preferably at least 80 mol%, most preferably at least 95 mol%.
  • the proportion of molecules with an ⁇ -permanent double bond (based on the number of all olefinically unsaturated macromolecules in a sample) is preferably at least 60 mol%, particularly preferably at least 75 mol%.
  • the proportions of the molecules with ⁇ and ⁇ double bonds can be determined by 1 H-NMR and / or 13 C-NMR spectroscopy, as is known to the person skilled in the art.
  • the polyisobutene obtained by the process according to the invention has a number average molecular weight Mn of 200 to 50,000, preferably 400 to 5,000, in particular 550 to 2,800.
  • Polyisobutenes with a number average molecular weight of less than 1500 typically have a dispersity of less than 1.7.
  • the fluorine content after removal of the diluent is typically less than 30 ppm, usually less than 15 ppm. In particularly preferred embodiments, the fluorine content is between the detection limit and 10 ppm. If desired, the fluorine content can be further reduced by treating the isobutene polymer with an inorganic adsorbent such as alumina.
  • PhSi (OEt) 3 phenyltriethoxysilane
  • the reactions were carried out in a 500 ml four-necked flask with a 250 ml dropping funnel with pressure equalization and a dry ice cooler, thermometer, septum and conduit for nitrogen gas.
  • Raffinate I of the composition given below was introduced via a flexible steel hose into a cooled receiver, which contained molecular sieve 3A, and liquefied with dry ice cooling.
  • the liquefied raffinate I was then transferred to the dropping funnel via a flexible steel hose.
  • the volume was measured by scaling the dropping funnel.
  • the catalyst complex was metered into the raffinate I placed in the four-necked flask using a disposable syringe.
  • Example 1 a solution of isobutene in hexane (50:50 vol. / Vol.) was used instead of raffinate I. The results are summarized in Table 1.
  • a reactor was used which consisted of a steel tube of 3 m in length and an inner diameter of 6 mm, over which 100 l / h of reactor contents were circulated through a gear pump.
  • the tube and pump had a volume of about 100 ml.
  • the Teflon tube and the pump head were placed in a cold bath of -25 ° C (cryostat).
  • Raffinate I (Examples 13 to 20) or isobutene / hexane solution (50:50 vol./vol .; Example 12) were fed in via a capillary with an internal diameter of 2 mm, which was precooled to -25 ° C. and on molecular sieve 3 A had been dried to less than 3 ppm water.
  • the catalyst complex was fed directly into the circulation on the suction side of the circulation pump.
  • reaction discharge was quenched with water in a mixing pump immediately after leaving the circulation. After the water phase had been separated off, the organic phase was passed over 3 A zeolite to dry.

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Abstract

L'invention concerne un procédé de fabrication de polymères d'isobutène uniquement éthyléniquement insaturés, la somme des proportions de molécules avec la double liaison en position α, et des molécules avec la double liaison en position β s'élevant à 75 % mol, par polymérisation de l'isobutène en phase liquide, en présence d'un complexe de catalyseur dissous ou dispersé qui comprend (i) un donneur d'électrons et, (ii) un composé de formule générale (I) Ha Meb [MFx]c (I), dans laquelle Me désigne un métal de degré d'oxydation m, M désigne un élément choisi parmi les éléments des groupes 2, 3, 4, 5, 10, 11, 13, 14 ou 15 de la Classification Périodique conforme à la notation IUPAC, d'indice d'oxydation n, a désigne un nombre entier ≥ 1, b désigne un nombre entier ≥ 0, x désigne un nombre entier ≥ 2, c désigne [(a + mb)/(x n)]. Comme catalyseur, on utilise de préférence HBF4 . O(CH3)2. Le procédé permet d'obtenir un polymère d'isobutène à faible teneur en fluor, même en utilisant des portions d'hydrocarbures en C4 techniques comme source d'isobutène.
PCT/EP2005/005093 2004-05-19 2005-05-11 Polymerisation d'isobutene en presence de complexes d'un donneur avec des acides fluores WO2005116094A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US11/597,274 US7932332B2 (en) 2004-05-19 2005-05-11 Isobutene polymerisation in the presence of a donor and fluorinated acids complex
DE502005010046T DE502005010046D1 (de) 2004-05-19 2005-05-11 Polymerisation von isobuten in gegenwart von komplexen von elektronendonoren mit fluor-haltigen säuren
EP05743534A EP1753793B1 (fr) 2004-05-19 2005-05-11 Polymerisation d'isobutene en presence de complexes de donneurs d'electrons avec des acides fluores
AT05743534T ATE476453T1 (de) 2004-05-19 2005-05-11 Polymerisation von isobuten in gegenwart von komplexen von elektronendonoren mit fluor- haltigen säuren

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EP04011971.1 2004-05-19
EP04011971A EP1598380A1 (fr) 2004-05-19 2004-05-19 Polymérisation d'isobutène en présence de complexes d'un donneur avec un acide contenant du fluor

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US20080214762A1 (en) * 2005-07-12 2008-09-04 Basf Aktiengesellschaft Method for the Production of High-Grade Polyisobutene
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GB486161A (en) 1936-03-24 1938-05-31 Bataafsche Petroleum A process for manufacturing products of high molecular weight soluble in mineral oils
WO1989001001A1 (fr) 1987-07-30 1989-02-09 The Lubrizol Corporation Polymeres d'alcenes inferieurs
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WO1995026814A1 (fr) 1994-03-31 1995-10-12 Exxon Chemical Patents Inc. Catalyseurs d'acides de lewis, sur support, derives de superacides pour reactions de conversion d'hydrocarbures.

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EP1753793A1 (fr) 2007-02-21
ATE476453T1 (de) 2010-08-15
US20070225459A1 (en) 2007-09-27
EP1598380A1 (fr) 2005-11-23
US7932332B2 (en) 2011-04-26
DE502005010046D1 (de) 2010-09-16

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